Flame retardant romp polycycloolefinic polymers

Patent metadata

Field	Value
Publication number	US-9765180-B2
Application number	US-201615086222-A
Country	US
Kind code	B2
Filing date	Mar 31, 2016
Priority date	Mar 31, 2015
Publication date	Sep 19, 2017
Grant date	Sep 19, 2017

Abstract

The present invention relates to certain ring open metathesis polymerized (ROMP) polymers encompassing polycycloolefinic monomers and a certain of olefinic monomers having thermally labile functional group. More specifically, the present invention relates to ROMP polymers under mass polymerization conditions of a series of functionalized norbornene-type monomers and at least one other olefinic monomer containing a thermally labile functional group such as, ether, acetal, ester, and the like. This invention also relates to reaction compositions containing a series of functionalized norbornene-type monomers and at least one other olefinic monomer containing a thermally labile functional group such as, ether, acetal, ester, and the like, which undergo ring open metathesis polymerization to produce materials which are useful as flame retardant materials having a variety of applications.

First claim

What is claimed is:

1. A ring opening metathesis polymerized (ROMP) polymer comprising one or more first type of repeating units represented by formula (IA), said first type of repeating unit is derived from a monomer of formula (I):

wherein:
denotes a place of bonding with another repeat unit;
a is an integer 0, 1 or 2;
R 1 , R 2 , R 3 and R 4 are the same or different and each independently of one another is selected from hydrogen, linear or branched (C 1 -C 16 )alkyl, hydroxy(C 1 -C 6 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl, perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl, di(C 1 -C 2 )alkylmaleimide(C 3 -C 6 )alkyl, di(C 1 -C 2 )alkylmaleimide(C 2 -C 6 )alkoxy(C 1 -C 2 )alkyl, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, and (C 1 -C 6 )acyloxy, where each of the aforementioned substituents are optionally substituted with a group selected from halogen or hydroxy; and
at least one second type of repeat unit derived from one of the monomers selected from the group consisting of:
a monomer of formula (II):

wherein:
at least one of R 5 , R 6 , R 7 and R 8 independently represents a group of formula (A):

wherein:
Z is selected from —CO—O—, —O—CO— and —O—CO—O—;
R 9 and R 10 are the same or different and each independently of one another is selected from linear or branched (C 1 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl and perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl;
R 11 is selected from substituted or unsubstituted (C 1 -C 6 )alkylene, (C 6 -C 10 )arylene (C 6 -C 10 )aryl(C 2 -C 6 )alkylene and (C 2 -C 6 )alkyl(C 6 -C 10 )arylene;
remaining one or more of R 5 , R 6 , R 7 and R 8 independently represents hydrogen, linear or branched (C 1 -C 12 )alkyl, hydroxy(C 1 -C 12 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl, perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryl, (C 5 -C 10 )heteroaryl(C 1 -C 3 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, and (C 1 -C 6 )acyloxy and halogen;
a monomer of formula (III):

wherein:
b is an integer from 2 to 6;
R 12 , R 13 , R 16 and R 17 are the same or different and each independently of one another is selected from hydrogen, linear or branched (C 1 -C 16 )alkyl, hydroxy(C 1 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 2 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl, perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl, di(C 1 -C 2 )alkylmaleimide(C 3 -C 6 )alkyl, di(C 1 -C 2 )alkylmaleimide(C 2 -C 6 )alkoxy(C 1 -C 2 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, and (C 1 -C 6 )acyloxy, where each of the aforementioned substituents are optionally substituted with a group selected from halogen or hydroxy; and
R 14 and R 15 are the same or different and each independently of one another is selected from linear or branched (C 1 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl and perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl; and
a monomer of formula (IV):

wherein:
c is an integer from 2 to 6;
Ar is (C 6 -C 10 )aryl; and
Z, R 9 , R 10 and R 11 are as defined above.

2. The ROMP polymer of claim 1 , wherein said one or more monomers of formula (I) is having:
a is 0 or 1;
at least one of R 1 , R 2 , R 3 and R 4 is selected from hydrogen, linear or branched (C 1 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl, and perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl; and
each of the remaining R 1 , R 2 , R 3 and R 4 is hydrogen.

3. The ROMP polymer of claim 1 , wherein said one or more monomers of formula (I) is selected from the group consisting of:
bicyclo[2.2.1]hept-2-ene (NB);
norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);
5-hexylbicyclo-[2.2.1]hept-2-ene (HexNB);
5-octylbicyclo[2.2.1]hept-2-ene (OctNB);
5-decylbicyclo[2.2.1]hept-2-ene (DecNB);
5-perfluorobutylbicyclo[2.2.1]hept-2-ene (C 4 F 9 NB);
5-phenethylbicyclo[2.2.1]hept-2-ene (PENB); and
2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (NBANB).

4. The ROMP polymer of claim 1 , wherein said one or more monomers of formula (I) are at least two distinct types of monomers of formula (I).

5. The ROMP polymer of claim 1 , wherein said polymer comprises one or more repeat units derived from corresponding monomers of formula (I) and a second type of repeat unit derived from a monomer of formula (II).

6. The ROMP polymer of claim 5 , wherein said second type of repeat unit derived from a monomer of formula (II) is having:
Z is —CO—O—;
R 9 and R 10 are the same or different and each independently of one another is selected from linear or branched (C 1 -C 10 )alkyl, perfluoro(C 1 -C 8 )alkyl, phenyl, naphthyl, benzyl, phenylethyl, perfluorophenyl and perfluorobenzyl;
R 11 is selected from substituted or unsubstituted (C 2 -C 4 )alkylene and phenylene;
remaining one or more of R 5 , R 6 , R 7 and R 8 independently represents hydrogen, linear or branched (C 1 -C 12 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl and perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl.

7. The ROMP polymer of claim 6 , wherein said second type of repeat unit is derived from a monomer of formula (II) selected from the group consisting of:

2-methylbut-3-en-2-yl bicyclo[2.2.1]hept-5-ene-2-carboxylate;

2-methylpent-4-en-2-yl bicyclo[2.2.1]hept-5-ene-2-carboxylate;

2-methylhex-5-en-2-yl bicyclo[2.2.1]hept-5-ene-2-carboxylate;

Assignees

• Promerus Llc

Inventors

• Ng Hendra
• Seto Keitaro
• Zhang Wei

Classifications

• C08G61/08 Primary

  of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring · CPC title

• C08G2261/592

  against heat · CPC title

• C08G2261/135

  Cross-linked structures · CPC title

• C08G2261/3324

  derived from norbornene · CPC title

• C08G2261/12

  Copolymers · CPC title